Issue 16, 2024

Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

Abstract

In the quest for sustainable ammonia synthesis routes, biomimetic complexes have been intensively studied. Here we focus on the Peter's group Fe-nitrogenase catalyst with EPPP scorpionate ligands, and explore the effect of anchor atom selection (B, Al, Ga, N and P) and the impact of chloro substitution on the phenyl rings on nitrogen fixation. The reaction profiles of complexes with Lewis basic anchor atoms exhibited energy-demanding reduction steps, with more exergonic protonation steps compared to the smoother reaction profiles observed for catalysts with Lewis acid anchor atoms, also implying that catalyst regeneration is especially challenging for catalysts with Lewis basic anchor atoms. The binding affinities of N2 and H2 to the complexes suggest that the autocatalytic hydrogen evolution reaction (HER), which ultimately leads to consumption of reactants and catalyst deactivation, is likely to become more prevalent for heavier anchor atoms and be more significant for Lewis basic anchor atom complexes. Out of the studied complexes, boron showed the smoothest reaction profile and the smallest affinity for H2, which supports its superiour role as an anchor atom in accordance with experimental data.

Graphical abstract: Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

Supplementary files

Article information

Article type
Paper
Submitted
01 Yan 2024
Accepted
07 Kul 2024
First published
11 Kul 2024

Phys. Chem. Chem. Phys., 2024,26, 12520-12529

Role of Lewis acid/base anchor atoms in catalyst regeneration: a comprehensive study on biomimetic EP3Fe nitrogenases

J. Kfoury and J. Oláh, Phys. Chem. Chem. Phys., 2024, 26, 12520 DOI: 10.1039/D4CP00483C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements